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Vol-2 Issue-3 2016 IJARIIE-ISSN(O)-2395-4396

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STUDY OF REMOVAL TECHNIQUES

FOR DYES BY ADSORPTION: A REVIEW

A.R.Warade1, R.W.Gaikwad2, R.S.Sapkal3 and V.S.Sapkal4

1 Associate Professor , Department of Chemical Engineering ,Pravara Rural Engineering College, Loni,

Dist: Ahmednagar (MS)-413736 , India 2 Professor & Head , Department of Chemical Engineering ,Pravara Rural Engineering College, Loni,

Dist: Ahmednagar (MS)-413736 , India 3 Professor, UDCT, SGB Amravati University, Amravati (MS)-India

3 Professor & Head, UDCT, SGB Amravati University, Amravati (MS)-India

ABSTRACT

Various dyes present in water have adverse effect on human life, plants and on animals. There are various

technologies used to effectively remove these dyes from effluent water. The methodology, advantages and

disadvantages of various technologies are discussed in detail. Adsorption of dyes, the matter of this review, is a

resourceful, low-cost and environmentally caring remedy for a host of pollutants. These may be of biological,

organic and inorganic in origin within water. The efficient and successful application of adsorption demands that

the pollutant, source of adsorbent are in close proximity or contact with each other. The ability of adsorption

technology to remove low levels of persistent organic pollutants as well as microorganisms in water has been widely

demonstrated and, progressively, the technology is now being commercialized in many areas of the world including

developing nations. This review considers recent developments in the research and application of adsorption for the

treatment of dyes in water. The review considers transport characteristics on the adsorbent surface, reactor design

and organic degradation. The effects of adsorption operating parameters on the process are discussed in addition.

Keywords: Dye removal, Adsorption, Biological, Chemical

1. INTRODUCTION

Various treatment methods are available for the removal of dyes from the wastewater. Many chemical, physical and

biological methods are generally used to remove dyes from the industria l effluent. Various chemical methods are

oxidative processes, H2O2-Fe (II) salts (Fenton’s reagent), and ozonation, photochemical, sodium hypo chloride

(NaOCl), cucurbituril and electrochemical destruction. Physical treatment methods for the removal of dye s are

adsorption, membrane filtration, ion exchange, irradiation and electro kinetic coagulation. The critical literature

review of all these methods is discussed in this paper.

1.1 Treatment Methods of Dyes

1.1.1 Chemical methods:

1.1.1.1 Oxidative processes:



This is the most commonly used method of decolonization by chemical means. This is mainly due to its simplicity

of application. The main oxidizing agent is usually hydrogen peroxide (H2O2) [Rosario et al., 2002]. This agent

needs to be activated by some means, for example ultra violet light. The methods of chemical decolonization vary

by the way in which the H2O2 is activated [Slokar and Marechal, 1997].Chemical oxidation removes the dye from

the dye-containing effluent by oxidation resulting in aromatic ring cleavage of the dye molecules [Raghavacharya,

1997].

1.1.1.2 H2O2-Fe (II) salts (Fentons reagent):

Fentons reagent is a suitable chemical means of treating wastewaters which are resistant to biological treatment or is

poisonous to live biomass [Slokar and LeMarechal, 1997]. Chemical separation uses the action of sorption or

bonding to remove dissolved dyes from wastewater and has been shown to be effective in decolorizing both soluble

and insoluble dyes. One major disadvantage of this method is sludge generation through the flocculation of the

reagent and the dye molecules. The sludge, which contains the concentrated impurities, still requires disposal. It has

conventionally been incinerated to produce power, but such disposal is seen by some to be far from environmentally

friendly. The performance depends on the final floc formation and its settling quality, although cationic dyes do not

coagulate at all. Acid, direct, vat, mordant and reactive dyes usually coagulate, but the resulting floc is of poor

quality and does not settle well, yielding mediocre results [Raghavacharya, 1997].

1.1.1.3 Ozonation:

The use of ozone was pioneered in the early 1970s, and it is a very good oxidizing agent due to its high instability

(oxidation potential, 2.07) compared to chlorine, another oxidizing agent (1.36), and H2O2 (1.78). Oxidation by

ozone is capable of degrading chlorinated hydrocarbons, phenols, pesticides and aromatic hydrocarbons [Lin and

Lin, 1993]. The dosage applied to the dye-containing effluent is dependent on the total color and residual COD to be

removed with no residue or sludge formation and no toxic metabolites [Gahr et al., 1994]. Ozonation leaves the

effluent with no color and low COD suitable for discharge into environmental waterways. This method shows a

preference for double-bonded dye molecules [Slokarand Marechal, 1997]. One major advantage is that ozone can be

applied in its gaseous state and therefore does not increase the volume of wastewater and sludge. A disadvantage of

ozonation is its short half-life, typically being 20 min. This time can be further shortened if dyes are present, with

stability being affected by the presence of salts, pH and temperature.

1.1.1.4 Photochemical:

This method degrades dye molecules to CO2 and H2O [Zamora et al., 1999] by UV treatment in the presence of

H2O2. Degradation is caused by the production of high concentrations of hydroxyl radicals. UV light may be used to

activate chemicals, such as H2O2, and the rate of dye removal is influenced by the intensity of the UV radiation, pH,

dye structure and the dye bath composition [Slokar and Marechal,1997; Rosario et al., 2002]. This may be set -up in

a batch or continuous column unit [Namboodri and Walsh, 1996]. Depending on initial materials and the extent of

the decolonization treatment, additional by-products, such as, halides, metals, inorganic acids, organic aldehydes and

organic acids may be produced. There are advantages of photochemical treatment of dye containing effluent like no

sludge is produced and foul odors are greatly reduced. UV light activates the destruction of H2O2 into two hydroxyl

radicals.

1.1.1.5 Sodium hypochlorite (NaOCl):

This method attacks at the amino group of the dye molecule by the Cl+. It initiates and accelerates azo bond

cleavage. This method is not suitable for dispersed dyes. An increase in decolonization is seen with an increase in Cl

concentration. The use of Cl for dye removal is becoming less frequent due to the negative effects, it has when

released into waterways [Slokar and Marechal, 1997] and the release of aromatic amines which are carcinogenic, or

otherwise toxic molecules [Banat et al.,1999].

1.1.1.6 Cucurbituril:

Cucurbituril was first mentioned by Behrand et al. [1905], and thenre discovered in the 1980s. It is a cyclic polymer

of glycoluril and formaldehyde [Karcher et al., 1999a, b]. Cucurbituril named, because its structure is shaped like a

pumpkin (member of the plant family Cucurbitaceous). The uril indicates that an urea monomer is also part of this

compound. Buchman [1992] showed extra ordinarily good sorption capacity of cucurbituril for various types of

textile dyes. Cucurbituril is known to form host-guest complexes with aromatic compounds and this may be the

mechanism for reactive dye adsorption. Another proposed mechanism is based on hydrophobic interactions or the

formation of insoluble cucurbituril dye-cation aggregates since adsorption occurs reasonably fast. To be industrially

feasible, Cucurbituril would need to be incorporated into fixed bed sorption filters [Karcher etal., 1999b]. The cost

of its application is a major disadvantage of this method.

1.1.1.7 Electrochemical destruction:

This is a relatively new technique, which was developed in the mid 1990s. It has some significant advantages for use

as an effective method for dye removal. There is little or no consumption of chemicals and no sludge build up.



Electro chemical methods have been successfully applied in the purification of several industrial wastewaters as well

as landfill leachate [Vlyssides et al. 1999]. The breaks down metabolites are generally not hazardous leaving it safe

for treated wastewaters to be released back into water ways. It shows efficient and economical removal of dyes and

a high efficiency for color removal and degradation of recalcitrant pollutants [Ogutveren and Kaparal, 1994;

Pelegrini et al., 1999]. Relatively high flow rates cause a direct decrease in dye removal, and the cost of electricity

used is comparable to the price of chemicals.

1.1.2 Physical treatments:

1.1.2.1 Adsorption:

Adsorption produces a high quality product, and is a process which is economically feasible [Choy et al., 1999].

Almost complete removal of impurities with negligible side effects explains its wide application in tertiary treatment

stages and polishing stages. Many researchers have studied the feasibility of using low cost materials, such as saw

dust (SD) [Naiya et al., 2009; Garg et al., 2003; Kalavathy and Miranda, 2010; Sharma et al., 2009; Ahmad et al.,

2009], waste orange peel[Namasivayam et al., 1996], bagasse fly ash [Mane et al., 2007a], rice husk ash [Maneet al.,

2007b], banana pith [Namasivayam et al., 1998], bottom ash [Gupta et al., 2004; Gupta et al., 2009; Mittal et al.,

2005], deoiled soya [Mittal et al., 2008], rice husk [McKay et al., 1986] and kaolin [Nandi et al., 2009]. The other

researchers also utilized adsorbents such as bentonite clay [Ramakrishna and Viaraghavan, 1997], neem leaf powder

[Bhattacharya and Sharma, 2003 and Bhattacharya and Sharma,2005], powdered activated sludge [Kargi and

Ozmıhc, 2004], perlite [Dogan and Alkan, 2004], powdered peanut hull [Gong et al., 2005], Natural and modified

clays like sepiolite [Mahir et al., 2005], zeolite [Armagan et al., 2004], bamboo dust[Kannan and Sundaram, 2001]

as low cost adsorbents. Other low cost adsorbents like coconut shell [Manju et al., 1998], groundnut shell [Kannan

and Sundaram, 2001], rice straw [Hameed and EI-Khaiary, 2008], duck weed [Waranusantigul et al., 2003],sewage

sludge [Otero et al., 2003], sawdust carbon [Jadhav and Vanjara, 2004],agricultural waste and timber industry waste

carbons [Bansal et al., 2009] and gram husk [Jain and Sikarwar, 2006] have used for removal of various dyes from

wastewaters. Critical review of low cost adsorbents for wastewater treatment has been presented by earlier

researchers [Gupta and Suhas, 2009; Mall et al., 1996; Bailey etal., 1999; Demirbas, 2009]. The table 2.1 gives the

summary of the literature review for removal of BG, CR and other dyes by adsorption technique.

1.1.2.2 Membrane filtration:

This method has the ability to clarify, concentrate and most importantly, to separate dye continuously from effluent

[Mishra and Tripathy, 1993]. It has some special features unrivalled by other methods; resistance to temperature, an

adverse chemical environment, and microbial attack. The concentrated residue left after separation poses disposal

problems and high capital cost and the possibility of clogging, and membrane replacement is its disadvantages. This

method of filtration is suitable for water recycling within a textile dye plant if the effluent contains low

concentration of dyes, but it is unable to reduce the dissolved solid content, which makes water re-use a difficult

task.

1.1.2.3 Ion exchange:

Ion exchange has not been widely used for the treatment of dye-containing effluents, mainly due to the opinion that

ion exchangers cannot accommodate a wide range of dyes [Slokar and Marechal, 1997]. Wastewater is passed over

the ion exchange resin until the available exchange sites are s aturated. Both cation and anion dyes can be removed

from dye-containing effluent this way. Advantages of this method include no loss of adsorbent on regeneration,

reclamation of solvent after use and the removal of soluble dyes. A major disadvantage of this method is cost.

Organic solvents are expensive, and the ion exchange method is not very effective for disperse dyes [Mishra and

Tripathy, 1993].

1.1.2.4 Irradiation:

Sufficient quantity of dissolved oxygen is required to break down the organic substances effectively by radiation.

The dissolved oxygen is consumed very rapidly and so a constant and adequate supply is required. This has an effect

on cost. Dye containing effluent may be treated in a dual-tube bubbling reactor. This method showed that some dyes

and phenolic molecules can be oxidized effectively at a laboratory scale only [Hosono et al., 1993]. In this study, the

possibility of using gamma rays to degrade or decolorize reactive dyes in water was investigated [Dilekand Olgun,

2002].

1.1.2.5 Electro coagulation:

Electro coagulation method utilizes direct current to produce sacrificial electrode ions, which removes undesirable

contaminants either by chemical reactions and precipitation or by causing colloidal materials to coalesce and then be

removed by electrolytic floatation. Electro coagulated sludge contains less bound water besides being more shear



resistant and readily filterable. The table 2.1 gives the summary of the literature review for removal of BG, CR and

other dyes by electro coagulation technique.

1.1.2.6 Coagulation flocculation:

It is one of the most popular conventional treatment methods. Polyelectrolytes are widely used coagulant aids as

cationic, anionic and non anionic additives. The sludge produced by polyelectrolyte is usually compact and easy to

dewater for subsequent treatment and disposal. It involves the addition of ferrous sulphate and ferric chloride,

allowing excellent removal of direct dyes from wastewaters. The optimum coagulant concentration is dependent on

the static charge of the dye in solute on and difficulty in removing the sludge formed as part of the coagulation is a

problem [Mishra and Tripathy, 1993]. Production of large amounts of sludge occurs, and this results in high disposal

costs [Gahr et al., 1994]. The table 2.1 gives the summary of the literature review for removal of BG, CR and other

dyes by coagulation/flocculation technique.

1.1.3 Biological treatments:

1.1.3.1 Decolonization by white-rot fungi:

White-rot fungi are able to degrade dyes using enzymes, such as lignin peroxides (LiP) or Manganese dependent

peroxidases (MnP). Other enzymes used for this purpose include H2O2-producing enzymes, such as, glucose-1-

oxidase andglucose-2-oxidase, along with laccase, and a phenoloxidase enzyme [Kirby, 1999].Thes e are the same

enzymes used for the lignin degradation. Azo dyes, the largest class of commercially produced dyes, are not readily

degraded by micro-organisms but these can be degraded by P. chrysosporium. Other fungi such as,

Hirschioporuslarincinus, Inonotushispidus, Phlebiatremellosa and Coriolusversi color have also been shown to

decolorize dye-containing effluent [Banat et al., 1996; Kirby, 1999].

1.1.3.2 Other microbial cultures:

Mixed bacterial cultures from a wide variety of habitats have also been shown to decolorize the diazo linked

chromospheres of dye molecules in 15 days [Knapp and Newby, 1995]. Nigam and Marchant [1995] and Nigam et

al., [1996] demonstrated that a mixture of dyes were decolorized by anaerobic bacteria in 24-30 h, using free

growing cells or in the form of bio films on various support materials. Ogawa and Yatome [1990] also demonstrated

the use of bacteria for azo dye bio degradation. These microbial systems have the drawback of requiring a

fermentation process, and are therefore unable to cope with larger volumes of textile effluents. Yeasts, such

asKlyveromycesmarxianus, are capable of decolorizing dyes. Banat et al., [1999] showed that K. marxianus was

capable of decolorizing Remazol Black B by 78-98%.Zissi et al., [1997] showed that Bacillus subtilis could be used

to break down p-aminoazo benzene, a specific azo dye. Further research using mesophilic and thermophilicmicrobes

have also shown them to degrade and decolorize dyes [Nigam et al., 1996; Banat et al., 1997].

1.1.3.3 Adsorption by living/dead microbial biomass:

The uptake or accumulation of chemicals by microbial mass has been termed Biosorption [Hu, 1996; Tsezos and

Bell, 1989]. Dead bacteria, yeast and fungi have all been used for the purpose of decolorizing dye-containing

effluents. The use of biomass has its advantages, especially if the dye-containing effluent is very toxic. Biomass

adsorption is effective when conditions are not always favorable for the growth and maintenance of the microbial

population [Modak and Natarajan, 1995].Adsorption by biomass occurs by ion exchange. Biosorption tends to occur

reasonably quickly: a few minutes in algae to a few hours in bacteria [Hu, 1996]. This is likely to be due to an

increase in surface area caused by cell rupture during autoclaving [Polman and Brekenridge, 1996].

1.1.3.4 Anaerobic textile-dye bioremediation systems:

Azo dyes make up 60-70% of all textile dyestuffs [Carliell et al., 1995]. Azo dyes are soluble in solution, and are not

removed via conventional biological treatments. Reactive dyes have been identified as the most problematic

compounds in textile dye effluents [Carliell et al., 1996, 1994]. A major advantage of this anaerobic system, apart

from the decolonization of soluble dyes, is the production of biogas. Biogas can be reused to provide heat and

power, and will reduce energy costs.

1.1.4 Studies on removal of Dyes using various treatment methods:

The table 1.1 gives the summary of the literature review for removal of BG, CR and other dyes by adsorption,

electro coagulation, electrochemical and coagulation/flocculation techniques.



Table1.1Studies on removal of Dyes using various treatment methods

References Process/Adsorbent Adsorbate/other

chemicals

Operating

conditions

Results and discussion

McKay et

al.,

1980a

Sorbsil silica Astra zone blue

Batch

Equilibrium time increases with increase in

concentration. Adsorption increases with

decrease in particle size. The rate-

controlling step is mainly intra particle

diffusion. Adsorption increased with

increase in temp. However adsorption

capacity decreased with increase in time.

Mckay et al.,

1980b

Silica Astra zone blue

(Basic blue 69)

Batch,

Fixed

and

Fluidized

Results indicate that silica has the ability to

remove considerable quantities of Astra

zone blue dye, BDST model is

inapplicable, C0=200 mg/l, pH=5.1.

Mckay et al.,

1980b

Silica

Astra zone blue

(Basic blue 69)

Batch,

Fixed

and

Fluidized

Results indicate that silica has the ability to

remove considerable quantities of Astra

zone blue dye, BDST model is

inapplicable, C0=200 mg/l, pH=5.1.

Mckay et al.,

1980c

Wood

Astra zone blue

and Telon blue

Batch

Adsorption of telon blue increased whereas

of astra zone blue decreased with rise of

solution temperature. Wood particle size

=150-25 m.

McKay et

al.,

1981

Peat

Astra zone blue

Batch

Adsorption increases with temp. Increase,

film diffusion to be the rate-controlling

step.

McKay et

al.,

1986

Wood bark, rice

husk, coal,

bentonite

clay, hair and

cotton waste

Sandolan,

Rhodamine,

Safranine, Congo

Foron Bril red,

Methylene blue,

Solar blue, Foron

blue

Batch

None of the adsorbents adsorbed sandolan

blue or sandolan Rhoda mine, Bentonite

was best overall, followed by tree bark,

cotton waste and rice husk, C0=50-1000

mg.

Gupta et al.,

1987

Coal (Singrauli)

53 m

Chrome dye

(Met omega

chrome orange)

Batch 100% at C0=5 and 80.77% at C0=20 mg/l.

The decrease in removal 97.66 to 71.09

with rise in temp. 30 to 50oC. C0=5-20

mg/1, Temp.=30 to 500C

Gupta et al.,

1988a

Fly ash

Chrome dye

(Metomega

chrome orange)

Batch

Higher removal at low pH concentration

and particle size. Rate controlling step is

mainly intra particle diffusion. C0=5-20

mg/1, pH=3.0-11.8, Particle size=53-300

m.

Gupta et

al.,1988b

Fly ash

Omega chrome

red dye

Batch

98.85% removal of dye in the acidic range.

pH=4.2, T= 300C, Dose =1.0 g, Volume=

50ml.

Gupta et al.,

1988c

China clay

Chrome dye

Batch

Batch First order reaction, diffusion controlled.

Mall et al.,

1994

Fly ash Bottom ash Methylene blue,

Methyl violet,

Scarlet,

Rhodamine B,

Acid orange, Sun

fast yellow,

Malachite green

Batch Higher carbon content bottom ash proved

more powerful adsorbent than fly ash.

Rhoda mine was most poorly adsorbed dye.

Contact time of 30-45 min. and pH 8 and

5.6



Mall et al.,

1995

Bottom ash Methylene blue,

Malachite

Green

Batch and

Column

Removal to the extent of 95 to 100 percent

in low concentration ranges and increase in

agitation gives higher removal.

Liversidge et

al.,1997

Linseed cake Basic Blue 41

Batch

The Langmuir equation described the

adsorption well. The enthalpy of adsorption

was found to be endothermic and the

capacity of the linseed cake for the dye

decreased with increasing temperature. The

linseed cake was compared with peat and it

was found that it had a greater capacity for

the dyestuff than peat.

Khattri et al.,

1998

Mixture of alumina

and clay (1:2)

Methylene blue,

Malachite green,

Crystal violet,

Rhodamine B

Batch

Maximum removal occurs in initial 35-40

min. With increase in initial concentration

from 6 -12 mg/1 of dye, the % removal

decreased. Optimum pH 7.2 and

temperature 250C. Batch: 2.0g adsorbent,

200 ml aqueous solution of dye, shaking

200 rpm.

Khattri et al.,

1999

Sagaun sawdust

Methylene blue,

Malachite green,

crystal violet,

Rhodamine B

Batch Maximum removal for Methylene blue

86%, Malachite green 83%, Rhodamine B

58%, Crystal violet 89%. At concentration

6 mg/1, pH 7.5, and 300C, 0.5 g/200ml

dose was used.

Vlyssides et

al., 1999

Electrochemical

Technique

Textile dye

wastewater

Batch

Textile dye wastewater TDW from a

reactive azo dyeing process was treated by

an electrochemical oxidation method using

Ti/Pt as anode and stainless steel 304 as

cathode. These results indicate that this

electrolytic method could be used for

effective TDW oxidation or as a feasible

detoxification and color removal

pretreatment stage for biological post

treatment.

Boon et al.,

1999

Coagulation/

flocculation

technique

Textile

wastewater

Batch

The effective range of pH for the

MgCl2treatment is between 10.5 and 11.0,

and beyond the range, the percentage of

color removal decreases tremendously.

Flocs formed by the MgCl2treatment are

found to give shorter settling time than the

alum and PAC treatment. The MgCl2

treatment has been used on the indus trial

dye waste, the removal rates of 97.9% for

coloring matter, 88.4% in COD and 95.5%

suspended solid can be achieved.

Polyelectrolyte, Koaret PA is commonly

used as a coagulant aid to improve the

coagulation process and subsequently the

floc settling velocity.

Chun and

Wang, 1999

Decolonization and

biodegradability of

photo catalytic

treated azo dyes

Reactive Yellow

KD-3G-,

Reactive red 15,

Reactive red 24

Batch

Greater than 90% of color removal of most

dyes solution was achieved after 20-30

min. treatment. COD and TOC in

wastewater were also reduced from 60% to

85%. It was found that BOD in wastewater

was increased after photo oxidation. This

indicates that the biodegradability of the

wastewater can be enhanced by photo



catalytic oxidation. The BOD/COD of

wastewater was generally more than 0.30

when their color disappeared completely.

The result implies that the optimal

exposing time to photocalatysis process is

the period for complete decolonization. The

photo catalysis process could be an

alternative for decolonization and further

color removal of dyes from wastewater as

pre-or post -treatment of conventional

biological process.

Buning

Chen et al.,

2001

Bagassepith

Acid Blue 25

(AB25), Acid

Red 114

(AR114), Basic

Blue 69 (BB69)

and Basic Red

22

Batch

C0=50-150mg/l. The equilibrium isotherms

of four adsorption systems of dyestuffs

(AB25, AR114, BB69 and BR22) on pith

can be formulated precisely by the

Langmuir equation. There are different

minimum values of the contact time for the

optimizations of a two-stage batch adsorber

system at different process conditions.

There is a significant difference among

these optimal results (minimum contact

time changes from 751 to 533 min for the

AB25–pith system, 959 to 672 min for the

BR22–pith system).

Dilek and

Olgun, 2002

By gamma

irradiation

Reactive Blue 15

and Reactive

Black 5

Batch

In this study, the possibility of using

gamma rays to degrade or decolorize

reactive dyes in water was investigated.

Two different reactive dyes (Reactive Blue

15 and Reactive Black 5) in aqueous

solutions were irradiated at doses of 0.1–15

kGy, at 2.87 and 0.14 kGy/h dose rates.

The COD reduction for all the dye

solutions was approximately 76–80% at 1

and 15 kGyfor RB5 and RB15.

Ghoreishi

and

Haghighi,

2003

Chemical catalytic

reaction and

biological

oxidation

Direct, Basic and

Reactive colors

Batch

The optimum dosage for treatment of

actual wastewater was found to be 50–60

mg/l for catalyst bisulfate and 200–250

mg/l for sodium boro hydride. Finally, a

bench-scale experimental comparison of

this technique with other reported

combined chemical–biological methods

showed higher efficiency and lower cost

for the new technique. The results of this

study indicate that a combined reduction–

biological treatment method is a viable

technique to effectively decrease the color,

BOD, COD and TSS by 74–88%, 97–100,

76–83 and 92–97%, respectively.

Georgiou et

al., 2003

Coagulation/

flocculation

techniques

Textile

wastewater

Batch

Lime (Ca(OH)2) and ferrous sulfate

(FeSO47H2O) of commercial grade were

utilized for the experimental procedure.

Treatment with lime alone proved to be

very effective in removing the color (70–

90%) and part of the COD (50–60%) from

the textile wastewater. Finally, the

treatment with lime in the presence of



increasing doses of ferrous sulfate was

tested successfully, however; it proved to

be very costly mainly due to the massive

production of solids that precipitated.

Sun et al.,

2003

Adsorption on

modified peat–resin

particle

Basic Magenta

and Basic

Brilliant Green

Batch C0=100-400mg/l, Agitation speed=200-

500rpm, particle size=0.8-5mm, The

adsorption isotherm showed that the

adsorption of basic dyes on modified peat–

resin particle deviated from the Langmuir

and Freundlich equations. The pseudo-first

order, pseudo-second order and

intraparticle diffusion models were used to

fit the experimental data. The change of

agitation speed did not cause significant

difference of intraparticle diffusion

parameter in experimental conditions.

Krishna et

al.,

2003

Adsorption on

Neem leaf powder

Brilliant Green

Batch

A novel adsorbent was developed from

mature leaves of natural Neem trees for

removing dyes from water. The pH of the

aqueous solutions of Brilliant Green was

6.5 which did not change much with

dilution. The dye solution is pH-sensitive,

it becomes turbid if the pH is lowered and

it changes color if the pH is increased.

Therefore, all the adsorption experiments

were done without adjusting the pH. The

adsorption experiments were conducted in

the concentration range of 2.07*10-2 to

10.36*10-2mmol/m3at four different

temperatures of 300, 303, 313 and 323 K

with adsorbent dose of 0.13–0.63 g/m3. If

the adsorbent dose was increased to 0.63

g/m3, the removal of the dye further

increased to 98%. The adsorption of the

dye, Brilliant Green, was found to be

endothermic indicating that the adsorption

would be enhanced if the temperature of

adsorption was a little above the ambient

temperature. However, adsorption at

ambient temperature was also substantial.

The values of the adsorption coefficients,

calculated from Langmuir and Freundlich

equations agree well with the conditions of

favorable adsorption.

Gulnaz et

al.,

2004

Activated sludge

Basic Red 18

and Basic

Blue 9

Batch The activated sludge had the highest dye

uptake capacity, having the monolayer

adsorption capacity 285.71 and 256.41

mg/g for Basic Red 18 and Basic Blue 9,

respectively, at pH value of 7.0 and 200C.

The equilibrium data fixed very well with

both the Langmuir and Freundlich models.

Garg et al.,

2004

Adsorbents

prepared from

Prosopis Cineraria

sawdust—an agro-

industry waste

Malachite green

Batch

The adsorbents included formaldehyde-

treated sawdust (PCSD) and sulphuric acid-

treated sawdust (PCSDC). Similar

experiments were carried out with

commercially available coconut based



carbon (GAC) to evaluate the performance

of PCSD and PCSDC. Adsorption

efficiency of different adsorbents was in

the order GAC>PCSDC>PCSD. An initial

pH of the solution in the range 6–10 was

favorable for the malachite green removal

for both the adsorbents. These experimental

studies have indicated that PCSD and

PCSDC could be employed as low-cost

alternatives in wastewater treatment for the

removal of dyes. Fixed adsorbent dose

(0.4g/100 ml), natural pH and at different

initial concentrations of malachite green

(50, 100, 150, 200 and 250 mg/l) for

different time intervals up to equilibrium

time (3h).

Xiang et al.,

2005

By reaction with

potassium

permanganate

Reactive , Direct

and Cationic

dyes

Batch

Decolonization of dye solutions by

potassium permanganate was studied.

When pH value <1.5, the decolonization

efficiency was very high. When pH value

>4.0, the dye solutions were almost not

decolorized by potassium permanganate.

Concentration of potassium permanganate

and temperature had significant effects on

the decolonization efficiency. The results

of the treatment of real wastewater by

potassium permanganate indicated that

oxidation of textile wastewater by

potassium permanganate might be used as a

pre-treatment process prior to biological

treatment.

Chakraborty

et al., 2005

Adsorption and

nano filtration

Reactive red

CNN

and reactive

black B

Batch

A combination of adsorption and nano

filtration (NF) was adopted for the

treatment of a textile dye house effluent

containing a mixture of two reactive dyes.

The effluent stream was first treated in a

batch adsorption process with sawdust as

an adsorbent to reduce the dye

concentration of the effluent by about 83%

for Dye 1 and 93% for dye 2. The effluent

from the adsorption unit was passed

through an NF unit for the removal of the

remaining small amount of dyes and to

recover the associated chemicals (mainly

salt) in the effluent stream. The dyes

remaining after this step were less than 1

ppm.

Chakraborty

et al., 2005

The adsorbent is

prepared from hard

wood saw dust

Crystal violet

Batch

It is seen that about 341mg of crystal violet

can be removed using 1g of the adsorbent

at 298K. Particle size of the adsorbent

(0.04–0.23mm), initial concentration of the

dye (75–200mg/1), temperature (288–

323K) and the amount of adsorbent (0.5–

2.0 g). All experimental runs are taken

using a high stirrer speed (2500rpm) and

neutral pH. Adsorption increases with



decrease in particle size, increase in

temperature at lower temperature.

Hosny et al.,

2005

By reaction with

hydrogen peroxide

Direct Green 28

and Direct

Blue 78

Batch

It is used in the current work to oxidize and

decolorize two of the direct dyes that fulfill

an outstanding demand. The oxidation

reaction of I showed a first order kinetics

for [H2O2] and zero-order kinetics for

[Dye]. The oxidation reaction of II showed

a first order kinetics for both [dye] and [Cu

(II)] and zero-order kinetics for [H2O2]

Garget al.,

2005

Indian Rosewood

sawdust: a timber

industry waste

Basic dye

(Methylene blue)

Batch

Optimum pH=7. Higher adsorption

percentages were observed at lower

concentrations of methylene blue.

Experiments were conducted with GAC,

SDC (Sulphuric acid treated sawdust

(SDC)) and SD (Formaldehyde treated

sawdust)at constant adsorbent dosage (0.4

g/100 ml), pH (neutral) and temperature

(26 0C) for 3 h by varying methylene blue

concentrations(50-500 mg/l).GAC has

more adsorption efficiency in comparison

to SDC and SD at all initial dye

concentrations studied. Decolonization of

wastewater was 100%, 92% and 87.1% by

GAC, SDC and SD, respectively, at 50

mg/l dye concentration.

Shaobin et

al.,

2005

Fly as hand red

mud

Methylene Blue

Batch

Fly ash generally shows higher adsorption

capacity than red mud. The results indicate

that the Redlich–Peterson model provides

the best correlation of the experimental

data. The adsorption is lower at pH less

than 7 and then is increased to higher

values at pH greater than 7. More

significant enhancement in the adsorption

of dye is reached at pH=10 than at pH=8.

Gupta etal.,

2006

Adsorption on

bottom ash and de

-oiled soya

Brilliant Blue

Batch and

Column

The batch studies clearly suggest that both

bottom ash and de-oiled soya exhibit

almost similar adsorption ability toward

Brilliant Blue FCF and can remove 100 to

90% of the dye in the concentration range

0.007 to 0.03 mM, at 30, 40 and 50 ◦C. The

results obtained are well fitted in the linear

forms of Freundlich and Langmuir

adsorption isotherms. Bulk removal of the

dye through column operations

recommends that bottom ash column

adsorbs quicker and more amount of dye

(about 95%) than de-oiled soya column

(about 79%).

Lopez et al.,

2006

Electrochemical

Technique

C.I. Reactive

Orange 4

Batch

Ti/PtOx electrodes were used to oxidize

simulated dye baths prepared with an

azo/dichlorotriazine reactive dye (C.I.

Reactive Orange 4). The decolonization

yield was dependent on the dyeing

electrolyte (NaCl or Na2SO4). Dyeing

effluents which contained from 0.5 to 20



g/1 of NaCl reached a high decolonization

yield, depending on the current density,

immediately after the electrochemical

process. These results were improved when

the effluents were stored for several hours

under solar light. After the electrochemical

treatment the effluents were stored in a

tank and exposed under different lighting

conditions: UV light, solar light and

darkness. The evolution of the

decolonization versus the time of storage

was reported and kinetic constants were

calculated. The time of storage was

significantly reduced by the application of

UV light.

Mall et al.,

2006

Adsorption on

Bagasse fly ash and

activated carbon

Congo Red

Batch

The effective pH0was 7.0 for adsorption on

BFA. Kinetic studies showed that the

adsorption of CR on all the adsorbents was

a gradual process. Equilibrium reached in

about 4 h contact time. Optimum BFA,

ACC and ACL dosages were found to be 1,

20 and 2 g/l, respectively. CR uptake by the

adsorbents followed pseudo-second-order

kinetics. Equilibrium isotherms for the

adsorption of CR on BFA, ACC and ACL

were analyzed by the Freundlich,

Langmuir, Redlich–Peterson, and Temkin

isotherm equations. Error analysis showed

that the R–P isotherm best-fits the CR

adsorption isotherm data on all adsorbents.

The Freundlich isotherm also shows

comparable fit. Thermodynamics showed

that the adsorption of CR on BFA was most

favorable in comparison to activated

carbons.

Mane etal.,

2007b

Adsorption on rice

husk ash

Brilliant Green

Batch

Optimum pH value of 3, adsorbent dose 6

g/l, equilibrium time 5h for the Co range of

50–300 mg/l. Adsorption of BG followed

pseudo-second-order kinetics. Intra-particle

diffusion does not seem to control the BG

removal process. Equilibrium isotherms for

the adsorption of BG on RHA were

analyzed by Freundlich, Langmuir,

Redlich–Peterson (R–P), Dubnin–

Radushkevich (D–R) and Temkin isotherm

models using a non -linear regression

technique. Langmuir and R–P isotherms

were found to best represent the data for

BG adsorption onto RHA. Adsorption of

BG on RHA is favorably influenced by an

increase in the temperature of the

operation. Values of the change in entropy

and heat of adsorption for BG adsorption

on RHA were positive. The high negative

value of change in Gibbs free energy

indicates the feasible and spontaneous



adsorption of BG on RHA.

Mane et al.,

2007a

Adsorption on

bagasse fly ash

Brilliant Green

Batch

Optimum conditions for BG removal were

found to be pH 3.0, adsorbent dose 3 g/l of

solution and equilibrium time 5h.

Adsorption of BG followed pseudo-second-

order kinetics. Redliche Peterson and

Langmuir isotherms were found to best

represent the data for BG adsorption onto

BFA. Adsorption of BG on BFA is

favorably influenced by an increase in the

temperature of the operation. Values of the

change in entropy and heat of adsorption

for BG adsorption on BFA were positive.

The high negative value of change in Gibbs

free energy indicates the feasible and

spontaneous adsorption of BG on BFA.

Batzias et

al.,

2007

Adsorption on

Sawdust

Methylene blue

Batch

The lower adsorption of methylene blue at

acidic pH is due to the presence of excess

H+

ions that compete with the dye cation

for adsorption sites. As the pH of the

system increases, the number of positively

charged sites decreases while the number

of the negatively charged sites increases.

The negatively charged sites favor the

adsorption of dye cation due to electrostatic

attraction. The increase in initial pH from

8.0 to 11.5 increases the amount of dye

adsorbed.

Minghua et

al.,

2007

Electrochemical

Technique

Cationic red X-

GRL; PbO2

anode electrode

and The

cathode was a

stainless steel

Batch

At low current density, the performance

would be cost-effective but need long

treatment time, while at high current

density it was of high efficiency but costly.

So that, current density of 2.0

mA/cm2would be a good choice.

Runping et

al.,

2007

Adsorption on rice

husk

Congo Red

Column

Thomas, Adams–Bohart, and Yoon–Nelson

models were applied to experimental data

to predict the breakthrough curves using

non-linear regression and to determine the

characteristic parameters of the column

useful for process design, while bed

depth/service time analysis (BDST) model

was used to express the effect of bed depth

on breakthrough curves. The results

showed that Thomas model was found

suitable for the normal description of

breakthrough curve at the experimental

condition, while Adams–Bohart model was

only for an initial part of dynamic behavior

of the rice husk column. The data were in

good agreement with BDST model. It was

concluded that the rice husk column can

remove CR from solution.

Jain

andSikarwar,

2007

Adsorption on

Sawdust

Congo Red

Batch

Specific rate constants of the processes

were calculated by kinetic measurements

and a first order adsorption kinetics was

observed in each case. Langmuir and



Freundlich adsorption isotherm models

were then applied to calculate

thermodynamics parameters as well as to

suggest the plausible mechanism of the

ongoing adsorption processes. In order to

observe the quality of wastewater COD

measurements were also carried out before

and after the treatments. A significant

decrease in the COD values was observed,

which clearly indicates that adsorption

method offer good potential to remove

Congo red from wastewater. Maximum

adsorption around 99 and 88% for activated

carbon and activated sawdust, respectively,

at pH 6.5. Activated sawdust is a cheap and

easily available material that thus can act as

a better replacement for activated carbon.

Alok et al.,

2007

Adsorption on De

-Oiled Soya a

waste of Soya oil

industries and

Bottom Ash a

waste of thermal

power plants

Methyl Orange

Batch and

Column

Optimum pH value of 3. Adsorption of the

dye over both the adsorbents has been

monitored through Langmuir and

Freundlich adsorption isotherm models and

feasibility of the process is predicted in

both the cases. For the two columns

saturation factors are found as 98.61 and

99.8%, respectively, for Bottom Ash and

De-Oiled Soya with adsorption capacity of

each adsorbent as 3.618 and 16.664 mg/g,

respectively.

Mittal et al.,

2008

Adsorption on

bottom ash and

deoiled soya

Brilliant Green

Batch

Sorption can be approximated more

appropriately by the pseudo-second-order

kinetic model than the first order kinetic

model for the adsorption of BG by SD. BG

adsorbed per unit mass of SD (qt) increased

with the increase in0C, although percentage

BG removal decreased with the increase in

C0

Mittal et al.,

2009

Adsorption on

deoiled soya

Congo

Red

Batch

Percentage CR removal decreased with the

increase in0C, although, CR adsorbed per

unit mass of SD (qe) increased with the

increase inC0

Nandi et al.,

2009

Adsorption on

Kaolin

Brilliant Green

Batch

Optimum pH value of 7, adsorbent dose 4

g/l and equilibrium time 4 h. The increase

in BG sorption capacity with the decrease

in temperature has also been reported. The

maximum adsorption capacity qm value of

65.42 mg/g for BG adsorption. The

exothermic adsorption. Removal increases

with increase in adsorbent dose. Sorption

can be approximated more appropriately by

the pseudo-second-order kinetic model than

the first-order kinetic model for the

adsorption of BG.

Lain et al.,

2009

Adsorption on

CaCl2modified

betonies

Congo Red

Batch




increase InC0.



Panda et al.,

2009

Adsorption on Jute

stick powder

Congo Red and

rhodamine B

Batch

The increase in CR sorption capacity with

the increase in temperature. Adsorption

kinetics was found to follow a second-order

rate expression.

Mittal et al.,

2009

Adsorption on

deoiled soya

Congo Red

Batch




increase in0C.

Ahmad et

al.,

2010

Adsorption on bael

shell carbon

Congo Red

Batch

Adsorption kinetics was found to follow a

second-order rate expression. Percentage

CR removal decreased with the increase

in0C, although, CR adsorbed per unit mass

of SD (qe) increased with the increase in0C.

The increase in CR sorption capacity with

the increase in temperature. The positive

value of H0indicates that the process is

endothermic in nature.

Afkhami et

al.,

2010

Adsorption on

Modified

maghemite nano

particles

Congo Red

Batch


second-order rate expression. The positive

value of H0indicates that the process is

endothermic in nature.

Hua et al.,

2010

Adsorption on

cattail root

Congo Red

Batch


second-order rate expression. It seems that

the intra-particle diffusion of CR dye into

pores is the rate-controlling step in the

adsorption process.

Khouni et

al.,

2011

Coagulation Blue Bezaktiv S-

GLD 150 and

Black Novacron

R

Batch

Coagulation/flocculation leads to a

maximum percent of color removal of

about 93% at 593 nm and 94% at 620 nm.

Merzouk et

al.,

2011

Chemical

Coagulation and

electro

C oagulation

techniques

Disperse red dye

Batch and

Continuous

Experimental results showed first that Al2

(SO4)3was far more effective than FeCl3for

color removal using CC, regardless of

operating conditions. A removal yield

higher than 90% could be achieved with a

40 mg/l dose of Al2(SO4)318H2O in a large

range of pH from 4 to 8 and for a dye

concentration up to 235 mg/l. The removal

yield could however be enhanced up to

95% using EC for pH values between 6 and

9 at the expense of higher operating costs.

Nevertheless, EC presented the additional

advantages to be more robust against pH

change and to reduce simultaneously

equipment costs in comparison to CC.

Lin et al.,

2011

Electrochemical

Technique

Active Orange

5R

Batch

RuOx–PdO–TiO2/Ti anode possesses

higher catalytic oxidation ability, as

compared to RuOx–PdO/Ti, in both direct

oxidation and indirect oxidation processes.

RuOx–PdO–TiO2/Ti could provide a

discoloration rate of 98.14% within 30 min,

while the COD removal could reach

51.43% in120min. It was indicated that

higher electro oxidation ability could be

achieved at RuOx–PdO–TiO2/Ti anode.



Rivera et al.,

2011

Electrochemical

Technique

Reactive Black 5

Batch

The decolorization of an azo dye, Reactive

Black 5 (RB5), by an electrochemical

technology was studied in both cubic and

cylindrical cell configurations, each with a

working volume of 0.4 L and graphite

electrodes. Low decolorization was

detected in the treatment of pure solutions

of RB5, but a significant extent of

decolorization was observed in the

presence of Na2SO4. Nearly complete

decolorization was achieved in 3 h for an

effluent containing 70 mg/l RB5 and 0.1M

Na2SO4, and the TOC removal was

approximately 95%. In the presence of the

non-inert electrolyte NaCl, complete

decolorization was detected. However, due

to the chloro-organic compounds formed in

the electrochemical oxidation with NaCl,

the TOC removal in the most optimal

conditions was approximately 93%.

Zhou et al.,

2011

Electrochemical

Technique

Methyl orange

Batch

High current density enhanced the

decolorization on both electrodes, but the

promotion on MMO was not as significant

as that on the BDD electrode, which led to

a sharp increase of specific energy

consumption. The decolorization of MO

performed better at acidic conditions for

two electrodes. High initial concentration

enhanced GCE though the COD and TOC

removal efficiency was decreased. The

GCE on BDD was much higher than that

on MMO, indicating that it was much more

efficient

Mane et al.,

2011

Adsorption on saw

dust

Brilliant Green

Batch


second-order rate expression. The

adsorption of BG onto SD was found to be

exothermic in nature. Adsorbent dose 4

g/L, equilibrium time 3 h for the Orange of

50–300 mg/l. Equilibrium adsorption data

for BG on SD were well represented by the

R-P and Temkin isotherm models.

Adsorption of BG on SD is favorably

influenced by a decrease in the temperature

of the operation. The adsorption capacities

of SD for BG dye were obtained as

58.4795, 55.8659and 52.6315 mg/g at288,

303 and 318 K, respectively. The negative

value of G0indicates spontaneous

adsorption of BG on SD. This study

concludes that the SD could be employed

as low-cost adsorbent for the removal of

BG dye from aqueous solution

Ghaedi et

al.,

2011

Adsorption on

activated carbon

prepared from

acorn

Brilliant Green

Batch

More than 90% removal efficiency was

obtained within 30 min at adsorbent dose

of 2 g/100ml for initial dye concentration

of 25 mg/l. The percentage of dye removal



remains almost constant within the pH

range of around 6–10. The adsorption of

dye was found to follow a pseudo-second-

order rate equation. Langmuir isotherm

model was fitted the best for the adsorption

system with an adsorption capacity of 2.11

mg/g of adsorbent. Adsorption capacity

increases with temperature.

2. CONCLUSIONS

During the last few years many articles discussed about the adsorption of dyes have been published. This evaluation

of literature describe diverse technologies for the removal of a range of dyes from the effluents. The environmental

troubles formed by the textile industries have received increased consideration for several decades because of

contaminated effluents, which mainly occur from dyeing processes. Lots of colored textiles and leather articles are

treated with azo dyes and pigments. This paper presented the effect of various physico-chemical experimental

conditions that will affect the dye adsorption such as solution pH, initial dye concentration, adsorbent dosage, and

temperature. The most important parameter is the solution pH, where a high pH value is preferred for cationic dye

adsorption while a low pH value is more suitable for anionic dye adso rption. For the effect of initial dye

concentration, the removal efficiency will decrease with an increase in the initial dye concentration due to the

saturation of adsorption sites on the adsorbent surface. It was also noticed that the dye removal efficie ncy increases

with increasing adsorbent dosage where the amount of sorption sites available for the adsorption of dye molecules

will increase by increasing the dose of adsorbent.

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